Hydroxy derivatives of diamantane, triamantane, and [121]tetramantane: Selective preparation of bis-apical derivatives

Article abstract of DOI:10.1002/ejoc.200700378

Functionalizations of diamantane, triamantane, and tetramantane with electrophihc reagents (Br₂, nitric acid) lead to various apical and medial disubstituted products that were separated and characterized individually. The highly desirable and otherwise inaccessible thermodynamically more stable apical bis-derivatives were obtained with high preparative yields through acid catalyzed isomerizations. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejoc.200700378

FULL PAPER
DOI: 10.1002/ejoc.200700378
Hydroxy Derivatives of Diamantane, Triamantane, and [121]Tetramantane:
Selective Preparation of Bis-Apical Derivatives[‡]
Natalie A. Fokina,[a] Boryslav A. Tkachenko,[a] Anika Merz,[a] Michael Serafin,[b]
Jeremy E. P. Dahl,[c] Robert M. K. Carlson,[c] Andrey A. Fokin,*[a,d] and
Peter R. Schreiner*[a]
Keywords: Cage compounds / Diamondoids / Hydroxylation / Isomerization / Nanostructures
Functionalizations of diamantane, triamantane, and tetra- stable apical bis-derivatives were obtained with high prepar-
mantane with electrophilic reagents (Br2, nitric acid) lead to
various apical and medial disubstituted products that were
separated and characterized individually. The highly desir-
able and otherwise inaccessible thermodynamically more
ative yields through acid catalyzed isomerizations.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
To develop molecule-based electronics it is particularly im-
portant to study charge transport across nanometer-scale
metal-molecule-metal junctions[6] at various locations of the
contact points.[7] Molecules which form assemblies with
predictable structures, well-defined attachment points, and
highly regular packing are of great value in nanofabrication
for the construction of nano-scale devices as well as in poly-
mer chemistry. In the case of self-assembled monolayers,[8,9]
chemical and physical properties of the molecular assem-
blies can lead to numerous applications.
Diamondoids, which resemble parts of the diamond lat-
tice, are very attractive nanoscale building blocks (0.5–
2 nm).[10] In contrast to CVD and detonation nanodiamond
materials, diamondoids are accessible as individual com-
pounds and allow precise structure-property correlation
studies. In particular, electron transport across molecular
wire junctions depends on molecular bridge properties and
requires analysis of the relationship between transport and
properties of the molecular species.[11] Diamondoids possess
conformationally rigid structures and their selective func-
tionalizations determine their potential use in nanofabri-
cation techniques as shown recently for adamantane (1)
(Figure 1).[12] 1-Adamantanethiolate SAMs demonstrated
properties useful in “microdisplacement printing”, where it
was used as a preassembled monolayer being well ordered
to protect the surface yet sufficiently labile to enable other
molecules to displace it through competitive adsorption.
These SAMs are considered as appealing matrices for mo-
lecular electronics.[9]
Introduction
In recent years considerable research has been focused
at the interface between organic chemistry and materials
sciences, specifically in the field of nanodiamond applica-
tions, ranging from microelectronics[1] to biologically com-
patible surfaces.[2] Diamond-based materials offer an excel-
lent set of properties, namely hardness, chemical stability,
high thermal conductivity, low density, and biocompat-
ibility.[3] Nanometer-sized diamonds (1.4–4.0 nm) are
known to be constituents of interstellar dusts and meteor-
ites, carbonaceous residues of detonations, and certain
types of diamond films produced by chemical vapor deposi-
tion (CVD). These nanodiamond materials are the subject
of a growing number of investigations.[4] However, nanodia-
monds from these sources cannot be obtained as completely
homogeneous materials with definite structures and particle
sizes.[5] Their subsequent functionalization produces aggre-
gates with broad size distributions, often with numerous in-
homogeneities with respect to surface functionalities.[5]
At the same time, progress in nanotechnology requires
functionalized structures assembled with atomic precision.
[‡] Functionalized Nanodiamonds, 8. Part 7: Ref.[30]
[a] Institut für Organische Chemie, Justus-Liebig University,
Heinrich-Buff-Ring 58, 35392 Giessen, Germany
Fax: +49-641-99-34309
E-mail: prs@org.chemie.uni-giessen.de
Andrey.Fokin@org.chemie.uni-giessen.de
[b] Institut für Anorganische und Analytische Chemie, Justus-Lie-
big University,
Heinrich-Buff-Ring 58, 35392 Giessen, Germany
[c] MolecularDiamond Technologies Chevron Technology Ven-
tures,
As a whole, the group of lower diamondoids includes
also diamantane (2) and triamantane (3), and higher dia-
mondoids start with tetramantane, which exists in three iso-
meric forms. Diamondoids are known to be present in
nearly all raw petroleum.[13] Adamantane and diamantane
100 Chevron Way, Richmond, CA 94802, USA
[d] Department of Organic Chemistry, Kiev Polytechnic Institute,
pr. Pobedy 37, 03056 Kiev, Ukraine
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
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Hydroxy Derivatives of Diamondoids
tetramantane (4) with 100% nitric acid in order to elaborate
the routes to their apical mono- and bis-hydroxy derivatives.
The advantages of this derivatization approach are scal-
ability, high yields, and predictable as well as adjustable
product compositions. The hydroxy diamondoid products
can be converted to a large variety of functionalized dia-
mondoids with well-defined attachment points.[22]
Figure 1. Diamondoids: adamantane (1), diamantane (2), triamant-
ane (3), and [121]tetramantane (4).
Results and Discussion
were the subjects of numerous investigations since their syn-
The selective preparation of apical derivatives of dia-
thesis.[12,14] Diamondoids 3 and 4 also are available synthet- mondoids is very challenging. Previously we showed that
ically in very small amounts,[15] however, extensive studies most C–H functionalizations lead predominantly to substi-
became possible only recently. Since they have been found tutions in the medial or “belt” positions.[18] Oxidation of
in sizeable quantities in oil, and have been isolated from diamondoids with 100% nitric acid affected only tertiary
some deep natural gas condensates,[16] the chemistry of positions, which we preliminarily demonstrated for hydro-
these hydrocarbons received a powerful stimulus.
carbons 2, 3, and 4.[17,18] Here, we show that their oxidation
The selective introduction of substituents to dia- with 100% nitric acid can be performed in a kinetically con-
mondoids is a challenging task owing to the large number trolled way, and that the nitroxy derivatives can be hy-
of similarly reactive tertiary C–H bonds. Previously, based drolyzed to the respective hydroxy compounds. The use of
on our computational predictions,[17] we showed experi- 100% nitric acid makes the processes technologically ef-
mentally the potential of electrophilic and oxidative trans- ficient, as the acid can be regenerated by distillation. More-
formations of these hydrocarbons.[18,19] The reactions of over, its practical value is reinforced by the fact that the
compounds 2, 3, and 4 with electrophilic reagents lead pre- process is metal- and halogen-free. The transformations of
dominantly to medial substitutions[18,20,21] with a selectivity hydrocarbons 2, 3, and 4 to the alcohols and diols has sub-
increase in the sequence 2–3–4. The utility of these results stantial advantages over bromination because the isomeric
is emphasized by the fact that free-radical approaches give hydroxy derivatives are easier to separate.[21,23]
mixtures of all possible tertiary and even secondary deriva-
Hydroxylation of Diamantane (2): En route to apical hy-
tives.[17] Apical derivatives of 3 and 4 can be prepared droxy derivatives of diamantane (2) we studied the reaction
through photooxidation with triplet diacetyl [CH3C(O)- of 2 with 100% nitric acid, which gave a mixture of mono-
C(O)CH3].[18,19] The steric hindrance at the medial posi- and dinitroxy derivatives. Subsequent isomerization of this
tions directs the course of these reactions and leads to api- mixture with sulfuric acid followed by hydrolysis gave 4-
cal mono- and diacetyl derivatives almost exclusively. How- hydroxydiamantane (6) as the major product (Scheme 1).
ever, photoacetylation has poor prospects as a preparative The alcohols 5 and 6 can be separated by column
method. Taking into consideration the potential of apical chromatography on silica gel or through recrystallization
derivatives for various applications, preparative approaches from cyclohexane or ethyl acetate; pure diol 7 can be fil-
are essential.
tered from the reaction mixture. Both nitroxy and hydroxy
Within the broader context of our studies in the field of derivatives can be isomerized with sulfuric acid; however,
hydrogen-terminated nanodiamonds (interchangeably used the nitroxy compounds are more soluble in sulfuric acid.
with the term “diamondoids”), we now present approaches Depending on the reaction time, isomerization of the mix-
that are amenable to the large-scale production of mono- ture of nitroxy diamantanes can lead either to the mixture
and bis-functionalized diamondoids. These approaches are of alcohols 5–7 enriched with the apical derivative 6, or to
based on the combination of kinetically and thermodynam- the almost exclusive formation of 4,9-dihydroxydiamantane
ically controlled C–H substitutions, and are in agreement (7, Scheme 1). Oxidation of 2 at longer reaction times al-
with our earlier computational predictions.[17] We studied lows to obtain the mixture dinitroxydiamantanes, where the
the oxidations of diamantane (2), triamantane (3), and [121]- 1,4-dinitroxydiamantane (8) dominates (Scheme 2).
Scheme 1. Nitroxylation of diamantane (2) and subsequent isomerization (all yields are preparative).
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Scheme 2. Preparation of 1,4-dihydroxydiamantane (9) via nitroxylation and subsequent hydrolysis.
After the reaction with 100% nitric acid, there are two nitric acid, the hydrolysis gave a mixture of triamantane
possibilities to isolate the 1,4-diamantane derivatives. The diols where 3,9-dihydroxy derivative 14 was the main prod-
first involves chromatographic separation of 1,4-dinitroxy- uct (46%, Scheme 4). This mixture was separated by col-
diamantane (8, 64%) from the mixture and its subsequent umn chromatography and diols 14–19 were characterized
hydrolysis to the target 1,4-diol (9). The second utilizes the individually.
hydrolysis of the mixture of dinitroxy derivatives followed
The structural assignments for diols 14–19 were made
by chromatographic separation of diol 9. We examined both based on their spectroscopic data. Diol 19 was identical to
ways and obtained 1,4-dihydroxydiamantane (9) in ca. 50% the standard sample obtained earlier as a result of consecu-
yield.
tive transformations, namely, photoacetylation of triamant-
Hydroxylation of Triamantane (3): After obtaining satis- ane (3), Baeyer–Villiger oxidation of 9,15-diacetyl triamant-
factory results with diamantane (2), we examined the appli- ane and subsequent hydrolysis.[18] The structure of diol 16
cability of this approach to larger diamondoids. The selec- was assigned based on the 13C NMR spectrum considering
tive functionalization of triamantane (3) represents a chal- the fact that this compound is the only one among the terti-
lenging task as the molecule has four different tertiary C– ary dihydroxy derivatives to have C2-symmetry. The struc-
H bonds. The reactivity of this hydrocarbon has not been tures of diols 14, 15, 17, and 18 were determined based on
studied well, and only some bromo derivatives were ob- comparison of the experimental and calculated (via in-
tained earlier.[20,24] Previously, we described the oxidation crements) 13C NMR spectra. Chemical shifts of each car-
of 3 with 100% nitric acid leading to three monohydroxytri- bon of the diols were calculated via increments obtained
amantanes with the OH group in the 2- (10), 3- (11), and from literature data[25] as well as those from the 13C NMR
9- (12) positions.[18] Here we present a procedure that ad- spectrum of 4-hydroxy triamantane (13, see above) for the
ditionally allows the separation of hitherto unknown 4-hy- C-4 hydroxy group. Values of the increments of 4-hydroxy-
droxytriamantane (13, Scheme 3).
triamantane (13) in the 13C NMR spectra are provided in
To the best of our knowledge, triamantane derivatives the Supporting Information (Figure S1). Additionally, we
functionalized at C-4 can be obtained only through the pro- confirmed the structure of Cs-symmetrical diol 17 by an X-
tocol presented here. The corresponding 4-bromide is ray analysis (Figure 2).
formed only in trace amounts in the reaction of 3 with neat
As expected from the selectivity of the mononitroxyl-
bromine for which the 2-substitution product dominates,[25] ation reaction, the diols with an OH group at C-3 (i.e., diols
while with HNO3 preferential formation of 3-hydroxytria- 14, 16, and 17) dominate in the reaction mixture. However,
mantane (11) was observed.[18] Thus, we assumed that 3- the kinetically controlled bis-functionalization of 3 is not
substituted derivatives must prevail in the disubstitution re- very selective, although the diol 14 forms as the main prod-
action. Indeed, at elongated reaction times with excess of uct. The most attractive bis-apical C2v-symmetrical diol 19
Scheme 3. Preparation of monohydroxy derivatives of triamantane (3).
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Hydroxy Derivatives of Diamondoids
Scheme 4. Kinetically controlled bis-substitution of triamantane (3) with nitric acid.
was obtained in only 4% yield via the kinetically controlled tributes to their energy difference (∆∆H298 = 5.4 kcal/mol,
dinitroxylation of 3. In order to estimate the possibility of for the relative ∆∆G298 values, geometries and xyz coordi-
increasing the selectivity through thermodynamically con- nates of optimized molecules see Supporting Information).
trolled isomerizations we computed the relative stabilities of As a result, the isomerization of the mixture of hydroxy
diols 14–19. We found that diol 17 is the least and diol 19 derivatives in 98% H2SO4 led to the selective formation of
is the most stable (∆∆G298 = 6 kcal/mol, B3PW91/6- the most thermodynamically stable diol 19 (Scheme 5). The
311+G**) among the isomers, and the enthalpy mostly con- latter, being highly symmetric, is minimally soluble in or-
Figure 2. The X-ray structure (50% probability) of diol 17 and its crystal packing.
Scheme 5. Thermodynamically controlled isomerization of triamantane diols.
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A. A. Fokin, P. R. Schreiner et al.
FULL PAPER
ganic solvents and was separated by filtration of the reac- vidually. The structures of Ci-symmetric diol 20 and dibro-
tion mixture in 79% preparative yield (Scheme 5).
mide 24 were confirmed by the 13C NMR spectroscopic
Alternatively, we obtained diol 19 directly from 3 data; the structure of dibromide 24 was additionally con-
(Scheme 6). The mixture of nitroxy derivatives obtained af- firmed by an X-ray analysis (Figure 3). The structures of
ter evaporation of nitric acid was isomerized in presence of the asymmetric diols 21–23 were assigned by comparing the
sulfuric acid to give diol 19 in 80% preparative yield. This chemical shifts of C–OH carbon atoms in their 13C NMR
approach may have technological advantages for the prepa- spectra with those of 2- and 6-hydroxytetramantanes de-
ration of 19 as it avoids photochemical oxidations and scribed previously[18] because the differences in these values
treatment with peracids.[17]
for the α-oxygen-substituted C atoms are quite characteris-
tic (73.8 vs. 68.4 ppm for C-2 and C-6 hydroxylated carbon
atoms, respectively). Diol 25 was identical to the one ob-
tained earlier via photooxidation of 4 with diacetyl, fol-
lowed by oxidation and hydrolysis.[18]
As expected from the mononitroxylation reaction, the
selectivity of the dinitroxylation is lower than that of the
brominations and different selectivities are observed. Thus,
in contrast to dibromination/hydrolysis products where me-
dial derivatives 20 and 21 dominate, dinitroxylation fol-
lowed by hydrolysis gave mostly apical derivatives 22 and
25. However, substantial amounts of other diols (20, 21,
and 23) were also present in the reaction mixture. The pre-
parative significance of this procedure was substantially im-
proved by subsequent isomerizations. After treatment of the
mixture of diols obtained either from bromination or ni-
troxylation with sulfuric acid, the bis-apical diol 25 was ob-
tained in 81 and 65% yields, respectively. This selectivity
is due to the higher thermodynamic stability of the apical
derivatives.
Scheme 6. One-pot preparation of bis-apical diol 19 from triamant-
ane (3).
Thus, while the kinetically controlled bis-functionaliza-
tion with HNO3 leads to a mixture enriched with belt-sub-
stituted triamantanes, the subsequent thermodynamically
controlled isomerization allows the selective preparation of
bis-apical diol 19.
Bis-Functionalization of [121]Tetramantane (4): As we
have shown recently, the mono-bromination of [121]tetra-
mantane (4) is highly selective and gives 2-bromo derivative
in 89% yield; as a consequence, 2-bromo derivatives domi-
The computed ∆∆G298 between the least stable diol 20
nate in the dibromination reaction mixture.[18] After its hy- and the most stable diol 25 is ca 3 kcal/mol at B3PW91/6-
drolysis in DMF/water we obtained a number of diols 20– 311+G**. Thus, thermodynamically controlled transforma-
23 as well as dibromide 24 (Scheme 7). The mixture was tions clearly favor diapical substitutions in higher dia-
separated and compounds 20–24 were characterized indi- mondoids.
Scheme 7. Bis-functionalizations of [121]tetramantane (4).
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Hydroxy Derivatives of Diamondoids
Figure 3. The X-ray structure of dibromide 24 and its crystal packing.
water, aq. satd. NaHCO3, brine, dried with Na2SO4 and concen-
trated under reduced pressure. CHCl3 and 96% H2SO4 were added
to the residue at 0 °C whilst stirring. The reaction mixture was
stirred at 0 °C and then at ambient temperature (for exact times of
stirring see the Supporting Information), poured onto ice and fil-
tered. The precipitate was washed with water and chloroform. The
filtrate was divided into organic and aqueous parts. The aqueous
part of the filtrate was percolated with ether for 24 h. The organic
phase of the filtrate was washed with water, aq. satd. NaHCO3,
brine, dried with Na2SO4. After solvent removal, a mixture was
separated by the column chromatography on silica gel.
1,4-Dinitroxydiamantane (8): Yield 64%. 1H NMR (400 MHz,
CDCl3, 25 °C): δ = 2.61 (m, 2 H), 2.41 (m, 1 H), 2.38 (m, 1 H),
2.21 (m, 3 H), 2.12 (m, 4 H), 2.04 (m, 1 H), 1.97 (m, 1 H), 1.94
(m, 1 H), 1.73 (AB, J = 13.4 Hz, 1.68 2 HA, 1.75 2HB) ppm. 13C
NMR (100 MHz, CDCl3, 25 °C): δ = 90.4 (C), 87.0 (C), 41.6 (CH),
39.1 (CH2), 39.0 (CH), 38.5 (CH), 38.0 (CH2), 35.3 (CH2), 34.4
Conclusions
Kinetically controlled dibrominations and dini-
troxylations of diamantane, triamantane, and [121]tetra-
mantane show markedly different selectivities. Medial bis-
derivatives dominate in the bromination reactions, while
apical products predominantly form in the nitroxylations.
The apical derivatives thermodynamically are 2–5 kcal/mol
more stable then the medial ones. This allows the selective
preparation of the bis-apical diamondoid derivatives
through acid-catalyzed rearrangements of mixtures of prod-
ucts obtained after the primary functionalizations.
Experimental Section
Computational Details: All computations were performed with the
GAUSSIAN03 program suite[26] utilizing analytical first and sec-
ond energy derivatives. Harmonic vibrational frequencies were
computed to ascertain the nature of all stationary points. The com-
puted enthalpies and free energies were not scaled. As several re-
cent studies have questioned the reliability of popular DFT meth-
ods for energy evaluations,[27] we used the B3PW91 functional as
more trustworthy for large molecules.[28]
(CH ), 29.7 (CH) ppm. IR (ν, CHCl ): = 2990 (C–H), 2860 (C–H),
˜
2
3
1610 (N=O), 1306 (N=O), 1250 (C–O), 1245 (C–O) cm–1.
1,4-Dihydroxydiamantane (7): Yield 47%. 1H NMR (400 MHz, [D6]-
DMSO, 22 °C): δ = 2.50 (br. s, 2 H), 2.06 (d, J = 11.8 Hz, 2 H),
1.94 (m, 1 H), 1.77 (m, 2 H), 1.69 (m, 1 H), 1.63 (m, 2 H), 1.60–
1.50 (m, 6 H) 1.46 (m, 2 H), 1.17 (d, J = 11.8 Hz, 2 H) ppm. 13C
NMR (100 MHz, [D6]DMSO, 22 °C): δ = 67.6 (C), 65.2 (C), 45.5
(CH2), 45.4 (CH2), 45.3 (CH), 40.0 (CH2), 38.5 (CH), 38.3 (CH),
36.2 (CH2), 29.5 (CH) ppm. MS: m/z (%) = 220 (35), 202 (100),
159 (11), 145 (44), 133 (5), 120 (9), 107 (49), 95 (18), 79 (14), 55
(12). Other physico-chemical characteristics of 1,4-dihydroxydia-
mantane (7) are identical to those previously reported.[29]
General Procedure for Hydroxylation of Diamondoids with Nitric
Acid: 100% HNO3 was added dropwise to a suspension of well
triturated diamondoid in CH2Cl2 at 0 °C whilst stirring. The reac-
tion mixture was stirred for 0.5 h at 0 °C and then at ambient tem-
perature (for exact times of stirring see Supporting Information).
Then the reaction mixture was diluted with water. Excess CH2Cl2
was distilled off and the residue was refluxed for 2 h, cooled and
extracted with CHCl3. The combined organic extracts were washed
with water, aq. satd. NaHCO3, brine, dried with Na2SO4. After
4-Hydroxytriamantane (13): Was obtained as a colorless solid, yield
1
7%, m.p. 224–226 °C (n-hexane). H NMR (200 MHz, CDCl3): δ
= 2.19 (m, 1 H), 2.12 (m, 1 H), 1.85 (m, 3 H), 1.71 (m, 6 H), 1.67
(m, 2 H), 1.61 (d, J = 3 Hz, 2 H), 1.59 (m, 2 H), 1.48 (m, 1 H),
1.42 (m, 1 H), 1.36 (m, 1 H), 1.32 (m, 2 H), 1.26 (m, 2 H) ppm.
13C NMR (50 MHz, CDCl3, 27 °C): δ = 70.1 (C), 49.0 (CH), 46.4
(CH2), 45.0 (CH2), 44.4 (CH2), 43.4 (CH), 39.3 (CH), 37.6 (CH),
37.2 (CH2), 33.0 (C), 32.5 (CH2), 27.5 (CH), 27.1 (CH) ppm. MS:
m/z (%) = 256 (10), 238 (100), 223 (2), 195 (2), 181 (3), 167 (8), 142
(10), 129 (8), 105 (5), 91 (8). HR-MS (m/z), found 256.1828; calcd.
for C18H24O: 256.1827. C18H24O (256.38): calcd. C 84.32, H 9.44;
found C 84.22, H 9.40.
solvent removal,
chromatography on silica gel.
a mixture was separated by the column
General Procedure for Hydroxylation of Diamondoids with Subse-
quent Isomerization: 100% HNO3 was added dropwise to a solution
of diamondoid in CH2Cl2 at 0 °C whilst stirring. The reaction mix-
ture was stirred for 0.5 h at 0 °C and then at ambient temperature
(for exact times of stirring see Supporting Information). Then the
reaction mixture was diluted with water. Excess CH2Cl2 was dis-
tilled off and the residue was refluxed for 2 h, cooled and extracted
with CHCl3. The combined organic extracts were washed with
3,9-Dihydroxytriamantane (14): Was obtained as a colorless solid,
yield 46%, m.p. 202–204 °C (chloroform). 1H NMR (400 MHz,
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A. A. Fokin, P. R. Schreiner et al.
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CD3OD, 23 °C): δ = 2.38 (m, 1 H), 2.25 (dt, J1 = 12.6, J2 = 3.3 Hz,
(2), 193 (2), 155 (6), 141 (15), 129 (14), 105 (11), 91 (18), 79 (6), 67
1 H), 2.04 (m, 1 H), 1.91 (m, 1 H), 1.81 (m, 1 H), 1.75–1.55 (m, 11 (5). C22H26Br2 (450.25): calcd. C 58.69, H 5.82; found C 58.54, H
H), 1.43–1.26 (m, 8 H) ppm. 13C NMR (50 MHz, CD3OD, 23 °C): 5.63.
δ = 71.8 (C), 68.5 (C), 52.6 (CH2), 52.0 (CH), 47.2 (CH2), 46.4
[121]Tetramantane-2,17-diol (20): Was obtained as a colorless solid,
(CH), 45.8 (CH2), 45.7 (CH2), 45.6 (CH2), 41.8 (CH), 41.4 (CH),
40.6 (CH), 39.5 (C), 38.3 (CH2), 35.8 (CH), 35.1 (CH), 32.9 (CH2),
31.9 (CH) ppm. MS: m/z (%) = 272 (5), 254 (100), 197 (7), 183 (3),
m.p. 247–248 °C (chloroform). 1H NMR (400 MHz, CDCl3,
22 °C): δ = 2.19–2.10 (m, 3 H), 2.10–2.06 (m, 1 H), 1.94–1.87 (m,
2 H), 1.80 (m, 2 H), 1.77 (m, 1 H), 1.75–1.67 (m, 5 H), 1.62–1.58
148 (9), 145 (17), 131 (7), 106 (10), 91 (5). HR-MS (m/z), found
(m, 1 H), 1.58–1.54 (m, 1 H), 1.50 (m, 2 H), 1.46 (m, 1 H), 1.44–
272.1754; calcd. for C18H24O2: 272.1776.
1.38 (m, 3 H), 1.37 (br. s, 2 H), 1.04 (dt, J1 = 12.5, J2 = 2.4 Hz, 2
2,9-Dihydroxytriamantane (15): Was obtained as a colorless solid,
yield 22%, m.p. 246–248 °C (chloroform). 1H NMR (200 MHz,
H), 0.98 (dd, J1 = 13.1, J2 = 3.0 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3, 22 °C): δ = 73.28 (COH), 54.28 (CH), 43.44
CD3OD, 22 °C): δ = 2.32–2.15 (m, 2 H), 1.96 (m, 1 H), 1.90 (m, 2 (CH), 39.44 (CH2), 39.17 (CH), 38.47 (C), 38.47 (CH2), 37.28
H), 1.85 (m, 1 H), 1.78 (m, 2 H), 1.75–1.62 (m, 10 H), 1.58 (m, 2 (CH2), 32.20 (CH2), 31.63 (CH), 26.89 (CH) ppm. MS: m/z (%) =
H), 1.49–1.33 (m, 2 H), 1.07–0.08 (m, 2 H) ppm. 13C NMR
324 (31), 306 (100), 289 (18), 193 (2), 179 (5), 144 (22), 129 (15),
(50 MHz, CD3OD, 23 °C): δ = 73.3 (C), 68.6 (C), 47.9 (CH), 47.4 105 (12), 91 (21), 79 (12), 55 (7). HR-MS (m/z), found 324.2082;
(CH2), 46.2 (CH2), 44.8 (CH), 41.6 (CH), 41.6 (CH), 40.8 (C), 40.7
(CH), 40.6 (CH2), 40.1 (CH2), 39.8 (CH), 39.2 (CH2), 38.8 (CH),
38.2 (CH2), 33.4 (CH2), 28.3 (CH) ppm. MS: m/z (%) = 272 (24),
254 (100), 196 (13), 158 (7), 145 (97), 129 (5), 107 (5), 91 (8). HR-
MS (m/z), found 272.1772; calcd. for C18H24O2: 272.1776.
calcd. for C22H28O2: 324.2089.
[121]Tetramantane-2,18-diol (21): Was obtained as a colorless solid,
1
m.p. 180–182 °C (hexane). H NMR (400 MHz, CDCl3, 24 °C): δ
= 2.36–2.30 (m, 1 H), 2.13–2.00 (m, 3 H), 1.92–1.86 (m, 1 H), 1.83–
1.77 (m, 1 H), 1.77–1.70 (m, 1 H), 1.69–1.60 (m, 5 H), 1.60–1.47
(m, 7 H), 1.47–1.17 (m, 7 H), 1.15 (br. s, 1 H), 1.06 (dt, J1 = 12.8,
J2 = 2.4 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ =
72.70 (COH), 70.29 (COH), 52.15 (CH), 51.64 (CH), 45.79 (CH2),
3,11-Dihydroxytriamantane (16): Was obtained as a colorless solid,
yield 12%, m.p. 278–280 °C (chloroform). 1H NMR (400 MHz,
CD3OD, 24 °C): δ = 2.34 (m, 2 H), 2.03 (m, 2 H), 1.92 (t, J =
2.4 MHz, 2 H), 1.72 (m, 1 H), 1.70–1.60 (m, 6 H), 1.56 (m, 1 H), 44.36 (CH2), 43.66 (CH), 43.31 (CH2), 42.82 (CH), 42.44 (CH),
1.53 (m, 1 H), 1.50 (m, 2 H), 1.40 (m, 1 H), 1.37 (m, 1 H), 1.28 (m,
39.41 (CH), 38.13 (CH2), 37.71 (CH2), 37.40 (C), 37.40 (CH), 36.62
4 H), 1.24 (m, 1 H) ppm. 13C NMR (100 MHz, CD3OD, 24 °C): δ (CH2), 34.76 (C), 33.77 (CH2), 33.36 (CH), 32.40 (CH2), 30.18
= 70.9 (C), 52.4 (CH), 47.1 (CH2), 45.2 (CH2), 41.8 (CH), 39.1 (C), (CH), 27.25 (CH) ppm. MS: m/z (%) = 324 (27), 306 (100), 288
38.1 (CH2), 34.7 (CH), 31.9 (CH), 27.8 (CH2) ppm. MS: m/z (%) (18), 278 (3), 265 (1), 176 (7), 163 (10), 129 (17), 117 (8), 105 (14),
= 272 (8), 254 (100), 236 (15), 213 (4), 165 (23), 145 (9), 106 (6), 91
91 (27), 79 (11), 55 (8). HR-MS (m/z), found 324.2068; calcd. for
(6). HR-MS (m/z), found 272.1772; calcd. for C18H24O2: 272.1776.
C22H28O2: 324.2089.
3,7-Dihydroxytriamantane (17): Was obtained as a colorless solid,
yield 6%, m.p. 277–279 °C (chloroform). 1H NMR (400 MHz,
[121]Tetramantane-2,6-diol (22): Was obtained as a colorless solid,
m.p. 213–215 °C (chloroform). 1H NMR (400 MHz, CDCl3,
CD3OD, 24 °C): δ = 2.50 (dt, J1 = 13.9 MHz, J2 = 3.0 MHz, 1 H), 25 °C): δ = 2.39–2.33 (m, 1 H), 2.14–2.07 (m, 1 H), 1.94–1.89 (m,
2.03 (m, 2 H), 1.85 (m, 2 H), 1.72–1.55 (m, 11 H), 1.40 (m, 1 H), 1 H), 1.87–1.54 (m, 15 H), 1.54–1.49 (m, 1 H), 1.48–1.41 (m, 1 H),
1.37–1.25 (m, 7 H) ppm. 13C NMR (100 MHz, CD3OD, 24 °C): δ
1.35 (m, 2 H), 1.33 (d, J = 3.2 Hz, 1 H), 1.29–1.21 (m, 2 H), 1.17
= 74.3 (C), 56.2 (CH), 46.5 (CH), 46.3 (CH2), 45.0 (CH2), 42.6 (br. s, 1 H), 1.03 (dt, J1 = 12.7, J2 = 2.5 Hz, 1 H), 0.98 (dd, J1 =
(CH), 40.9 (CH), 40.1 (C), 37.9 (CH2), 31.6 (CH), 29.3 (CH2) ppm. 12.9, J2 = 2.9 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C):
MS: m/z (%) = 272 (53), 254 (100), 236 (53), 195 (5), 183 (5), 165 δ = 73.76 (COH), 68.25 (COH), 51.42 (CH), 51.17 (CH2), 48.71
(17), 155 (10), 145 (19), 129 (33), 117 (16), 106 (33), 91 (38). HR-
MS (m/z), found 272.1759; calcd. for C18H24O2: 272.1776.
C18H24O2 (272.38): calcd. C 79.37, H 8.88; found C 79.40, H 8.84.
(CH), 45.70 (CH), 44.83 (CH2), 44.80 (CH2), 44.80 (CH2), 43.95
(CH), 40.08 (CH), 39.52 (CH), 38.84 (CH2), 38.36 (CH2), 38.20
(C), 37.83 (CH), 37.68 (CH2), 35.27 (CH), 35.00 (C), 34.72 (CH),
32.35 (CH2), 27.28 (CH) ppm. MS: m/z (%) = 324 (11), 306 (100),
290 (3), 265 (5), 233 (2), 221 (2), 195 (2), 171 (3), 142 (24), 129
(14), 115 (10), 105 (10), 91 (25), 79 (13), 55 (8). HR-MS (m/z),
found 324.2069; calcd. for C22H28O2: 324.2089.
4,9-Dihydroxytriamantane (18): Was obtained as a colorless solid,
yield 4%, m.p. 219–221 °C (chloroform). 1H NMR (400 MHz,
CD3OD, 25 °C): δ = 2.50 (br. d, J = 12.8 MHz, 2 H), 1.91 (m, 2
H), 1.81 (m, 1 H), 1.77 (m, 1 H), 1.74–1.61 (m, 10 H), 1.59 (m, 2
H), 1.42 (m, 1 H), 1.39 (m, 1 H), 1.35 (m, 2 H), 1.32 (m, 2 H) ppm. [121]Tetramantane-2,13-diol (23): Was obtained as a colorless solid,
13C NMR (50 MHz, CD3OD, 24 °C): δ = 74.3 (C), 68.4 (C), 52.6 m.p. 199–201 °C (chloroform). 1H NMR (400 MHz, CDCl3,
(CH2), 49.3 (CH), 46.6 (CH2), 46.2 (CH2), 45.4 (CH2), 43.8 (CH), 25 °C): δ = 2.23–2.03 (m, 4 H), 1.92–1.87 (m, 1 H), 1.86–1.76 (m,
41.5 (CH), 39.6 (CH), 36.5 (C), 33.4 (CH2), 28.1 (CH) ppm. MS:
3 H), 1.76 (AB, JAB = 12.1 Hz, 1 H), 1.65 (br. s, 3 H), 1.60–1.49
m/z (%) = 272 (13), 254 (100), 196 (3), 159 (4), 145 (10), 129 (5), 109 (m, 6 H), 1.48–1.30 (m, 6 H), 1.31 (AB, JAB = 12.8, J2 = 3.1 Hz, 1
(11), 91 (9). HR-MS (m/z), found 272.1781; calcd. for C18H24O2:
272.1776.
H), 1.24 (AB, JAB = 12.8, J2 = 3.1 Hz, 1 H), 1.12–1.04 (m, 1 H),
0.96 (AB, JAB = 12.1 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3,
25 °C): δ = 73.16 (COH), 70.44 (COH), 54.96 (CH), 49.01 (CH),
48.77 (CH), 47.58 (CH2), 44.39 (CH2), 43.63 (CH2), 43.28 (CH),
42.96 (CH), 39.44 (CH), 39.33 (C), 38.32 (CH2), 37.74 (CH), 37.64
(CH2), 37.08 (CH), 34.79 (C), 32.43 (CH2), 31.90 (CH2), 31.80
(CH2), 26.79 (CH), 26.59 (CH) ppm. MS: m/z (%) = 324 (30), 306
(100), 288 (11), 277 (3), 217 (2), 193 (3), 179 (5), 158 (10), 144 (16),
129 (15), 117 (9), 105 (11), 91 (32), 77 (9), 55 (9). HR-MS (m/z),
found 324.2074; calcd. for C22H28O2: 324.2089.
2,17-Dibromo[121]tetramantane (24): Was obtained as a colorless
solid, yield 17%, m.p. 230–232 °C (chloroform). 1H NMR
(400 MHz, CDCl3, 25 °C): δ = 2.71 (br. s, 2 H), 2.58 (dq, J1 = 13.1,
J2 = 3.2 Hz, 2 H), 2.24 (t, J = 2.1 Hz, 2 H), 2.16 (m, 2 H), 2.01–
1.94 (m, 4 H), 1.94–1.90 (m, 2 H), 1.89–1.83 (m, 2 H), 1.82–1.66
(m, 4 H), 1.60 (dq, J1 = 13.1, J2 = 2.7 Hz, 2 H), 1.25–1.15 (m, 4
H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ = 89.51 (CBr),
58.91 (CH), 48.10 (CH), 42.74 (C), 41.26 (CH2), 40.29 (CH), 40.15
(CH2), 38.30 (CH2), 34.86 (CH2), 34.67 (CH), 26.88 (CH) ppm.
Supporting Information (see also the footnote on the first page of
MS: m/z (%) = 371 (99), 369 (100), 325 (4), 307 (3), 289 (16), 233 this article): The exact procedures for functionalization of dia-
4744 Eur. J. Org. Chem. 2007, 4738–4745
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Hydroxy Derivatives of Diamondoids
mondoids 2, 3 and 4, the increments for the NMR 13C chemical
shifts of compound 13, the optimized geometries and computed
relative energies of triamantane diols, as well as details of the X-
ray structural study are available.
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Received: April 27, 2007
Published Online: July 19, 2007
Eur. J. Org. Chem. 2007, 4738–4745
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4745